EP1648898A1 - Derives de pyrazolidine-dione a substitution hetaryl avec les caracteristiques d'herbicides - Google Patents

Derives de pyrazolidine-dione a substitution hetaryl avec les caracteristiques d'herbicides

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Publication number
EP1648898A1
EP1648898A1 EP04763173A EP04763173A EP1648898A1 EP 1648898 A1 EP1648898 A1 EP 1648898A1 EP 04763173 A EP04763173 A EP 04763173A EP 04763173 A EP04763173 A EP 04763173A EP 1648898 A1 EP1648898 A1 EP 1648898A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
optionally
compounds
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04763173A
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German (de)
English (en)
Inventor
Reiner Fischer
Lutz Assmann
Stefan Lehr
Mark Wilhelm Drewes
Dieter Feucht
Olga Malsam
Guido Bojack
Thomas Auler
Martin Jeffrey Hills
Heinz Kehne
Christian Arnold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Filing date
Publication date
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Publication of EP1648898A1 publication Critical patent/EP1648898A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to new hetaryl-substituted pyrazolidinedione derivatives, several processes for their preparation and their use as pesticides and / or herbicides.
  • the invention also relates to new selective herbicidal active compound combinations which contain hetaryl-substituted pyrazolidinedione derivatives on the one hand and at least one compound which improves crop compatibility on the other hand and can be used with particularly good success for selective weed control in various crop plants.
  • a for hydrogen in each case optionally substituted by halogen, alkyl, alkenyl or
  • D represents hydrogen or an optionally substituted radical from the series Al yl
  • a and D together with the atoms to which they are attached represent a saturated or unsaturated and optionally at least one heteroatom-containing cycle which is unsubstituted or substituted in the A, D part, for hydrogen (a) or for one of the group
  • E represents a metal ion equivalent or an ammonium ion
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • Rl for each optionally substituted by cyano or halogen alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally substituted by halogen, alkyl or alkoxy cycloalkyl which is substituted by at least one
  • Hetero atom can be interrupted, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
  • R ⁇ represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or in each case optionally substituted cycloalkyl, phenyl or benzyl,
  • R ⁇ represents alkyl, haloalkyl or optionally substituted phenyl or benzyl
  • R4 and R5 independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio and represent optionally substituted phenyl, benzyl, phenoxy or phenylthio,
  • R6 and R ⁇ independently of one another represent hydrogen, in each case optionally substituted by halogen substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, optionally substituted phenyl, optionally substituted benzyl, or together with the N atom to which they are attached represent a cycle which may be interrupted by oxygen or sulfur.
  • the compounds of the formula (T) can be present as regioisomers, as geometric and / or optical isomers or isomer mixtures, in different compositions, which can optionally be separated in a customary manner. Both the pure isomers and the isomer mixtures, their preparation and use, and agents containing them are the subject of the present invention. However, for the sake of simplicity, the following always refers to compounds of the formula (I), although both the pure compounds and, if appropriate, mixtures with different proportions of isomeric compounds are meant.
  • X represents alkyl, halogen, haloalkyl or optionally substituted phenyl
  • Y represents hydrogen, alkyl or halogen
  • Z represents alkyl, hydroxy, alkoxy, haloalkoxy, in each case optionally substituted phenylalkyloxy, heterarylalkyloxy or cycloalkyl.
  • A, D, G, X, Y and Z have the meaning given above.
  • A, D, E, L, M, X, Y, R 1 , R 2 , R 3 , R ⁇ , R 5 , R 6 and R 7 have the meanings given above.
  • A, D, E, L, M, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the meanings given above. Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (1-3 -a) to (1 -3 -g) when Het represents group (C),
  • A, D, E, L, M, X, Y, Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the meanings given above.
  • A, D, E, L, M, X, Y, Z, R 1 , R 2 , R 3 , R 4 R 5 , R 6 and R 7 have the meaning given above.
  • Rl has the meaning given above and
  • Rl has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
  • chloroformic acid esters or chloroformic acid thioesters of the formula (VIH) are chloroformic acid esters or chloroformic acid thioesters of the formula (VIH),
  • R 3 has the meaning given above
  • Me for a mono- or divalent metal preferably an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium
  • an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium
  • Rl0 ; R11 9 R12 independently of one another represent hydrogen or alkyl (preferably C 1 -C 6 -alkyl),
  • the new compounds of the formula (I) have very good activity as pesticides, preferably as insecticides and / or acaricides and / or herbicides.
  • a 1 represents one of the divalent heterocyclic groupings outlined below,
  • a 2 represents alkanediyl which has 1 or 2 carbon atoms and is optionally substituted by C 1 -C 4 -alkyl and or CC 4 -alkoxy-carbonyl,
  • R 22 represents hydroxy, mercapto, amino, -C 6 alkoxy, C 6 alkylthio, C 6 alkylamino or di (C 4 alkyl) amino,
  • R 23 represents in each case optionally substituted by fluorine, chlorine and / or bromine -CC 4 alkyl,
  • R 24 represents hydrogen, each optionally substituted by fluorine, chlorine and / or bromine -Qi-alkyl, C 2 -C.-alkenyl or C 2 -C 6 -alkynyl, Cr -alkoxy- -G t -alkyl, dioxolanyl-C C 4 -alkyl, furyl, furyl-C C -alkyl, thienyl, thiazolyl, piperidinyl, or phenyl optionally substituted by fluorine, chlorine and or bromine or CC-alkyl,
  • R 25 for hydrogen, each optionally substituted by fluorine, chlorine and or bromine - alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, CrC 4 alkoxy-C C 4 -alkyl, dioxolanyl-C
  • R 25 represents hydrogen, cyano, halogen, or C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or phenyl which is optionally substituted by fluorine, chlorine and / or bromine,
  • R 27 represents hydrogen, optionally substituted by hydroxy, cyano, halogen or CC alkoxy, CC 6 alkyl, C 3 -C 6 cycloalkyl or tri- (C r C 4 alkyl) silyl,
  • R 28 represents hydrogen, cyano, halogen, or C r C 4 -alkyl, C 3 -C 6 -cycloalkyl or phenyl which are each optionally substituted by fluorine, chlorine and / or bromine,
  • X 1 represents nitro, cyano, halogen, C 1 -C 4 -alkyl, - -haloalkyl, C 1 -C 4 -alkoxy or CC - haloalkoxy,
  • X 2 represents hydrogen, cyano, nitro, halogen, CC 4 -alkyl, C 4 haloalkyl, CC 4 -alkoxy or CC is 4 haloalkoxy,
  • X 3 represents hydrogen, cyano, nitro, halogen, CC 4 alkyl, CC 4 haloalkyl, C 1 -C 4 alkoxy or C r C 4 haloalkoxy,
  • n stands for a number between 0 and 5
  • R 29 represents hydrogen or C 1 -C 4 alkyl
  • R 30 represents hydrogen or -CC alkyl
  • R 31 for hydrogen in each case optionally substituted by cyano, halogen or -CC alkoxy CC 6 alkyl, Ci-C ⁇ -alkoxy, C r C 6 -alkylthio, -C-C 6 alkylamino or di- (CC 4 alkyl ) - amino, or in each case optionally substituted by cyano, halogen or -CC 4 alkyl C 3 -C ⁇ cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio or C 3 -C 6 cycloalkylamino stands,
  • R 32 represents hydrogen, optionally cyano-, hydroxyl-, halogen or C ⁇ -C 4 -alkoxy-substituted C ⁇ -C 6 -alkyl, in each case optionally cyano- or halogen-substituted C 3 -C 6 - alkenyl or C 3 -C 6 alkynyl, or optionally cyano-, halogen or C r C 4 -alkyl-substituted C 3 -C 6 cycloalkyl,
  • X 4 represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, CC 4 -alkoxy or CC -haloalkoxy, and
  • X 5 represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, halogen, C 1 -C 4 -alkyl, CC 4 -haloalkyl, C 1 -C 4 -alkoxy or CC -haloalkoxy.
  • Het preferably stands for
  • X preferably represents C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, optionally by halogen,
  • Y preferably represents hydrogen, C 6 -C 6 -alkyl, chlorine or bromine,
  • Z is preferably Ci-Cg-alkyl, hydroxy, C ⁇ -C 6 -alkoxy, C 6 -haloalkoxy or in each case optionally substituted by C ⁇ -C 6 -alkyl, C 6 -alkoxy, halogen, C] -C - haloalkyl,
  • Ci-C ⁇ -haloalkoxy cyano or nitro substituted phenyl-C 2 -alkyloxy or Hetaryl -CC 2 alkyloxy or C 3 -C 6 cycloalkyl optionally substituted by CrC 2 alkyl or halogen,
  • A preferably represents hydrogen, in each case optionally substituted by halogen
  • D preferably represents hydrogen, in each case optionally substituted by halogen C 1-4
  • Ci-CKj-alkoxy-Ci-Cg-al l poly-Cj-Cg-alkoxy-Ci -CG-alkyl, C ⁇ -C 0-Alkylthio-C2-Cg-alkyl, optionally substituted by halogen, Ci - C-4-alkyl, -C -C-haloalkyl, -C -C4-alkoxy or -C -C-haloalkyl C3-Cg-cycloalkyl, in which optionally a Ring member is replaced by oxygen or sulfur or in each case optionally by halogen, Ci-Cg-alkyl, C ⁇ -Cg-
  • Haloalkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, cyano or nitro substituted phenyl, hetaryl with 5 or 6 ring atoms for example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl
  • phenyl-Ci -Cg-alkyl or hetaryl-Ci -Cg-alkyl with 5 or 6 ring atoms for example furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl
  • a and D together preferably represent in each case optionally substituted C -Cg-alkanediyl or Cß-Cg-alkenediyl, in which a methylene group is optionally replaced by nitrogen, oxygen or sulfur and
  • Halogen hydroxy, mercapto or in each case optionally substituted by halogen
  • G preferably represents hydrogen (a) or one of the groups
  • E represents a metal ion equivalent or an ammonium ion
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • Rl preferably represents in each case optionally substituted by halogen -CC-C2 () alkyl, C -C 2 o-alkenyl, Ci-Cg-Alko y-Ci-Cg-alkyl, Ci-Cg-alkylthio-Ci-Cg-alkyl, Poly-Ci-Cg-alkoxy-Ci-Cg-alkyl or optionally by halogen, Ci-Cg-alkyl or Ci-Cg-alkoxy substituted C 3 -Cg cycloalkyl in which one or more (preferably not more than two) ring members which are not directly adjacent are optionally replaced by oxygen and / or sulfur,
  • phenyl optionally substituted by halogen, cyano, nitro, Ci-Cg-alkyl, Ci-Cg-alkoxy, Ci-C - haloalkyl, Ci-Cg-haloalkoxy, Ci-Cg-alkylthio or Ci-Cg-alkylsulfonyl,
  • phenyl-Ci-Cg-alkyl optionally substituted by halogen, nitro, cyano, Ci-Cg-alkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkyl or Ci-Cg-haloalkoxy,
  • Ci-Cg-alkyl for 5- or 6-membered hetaryl optionally substituted by halogen, Ci-Cg-alkyl, Ci-C2-haloalkyl or Ci-C4-alkoxy (for example pyrazolyl, thiazolyl, pyridyl,
  • phenoxy-Ci-Cg-alkyl optionally substituted by halogen or Ci-Cg-alkyl or
  • hetaryloxy-Ci-Cg-alkyl optionally substituted by halogen, amino or Ci-Cg-alkyl (for example pyridyloxy-Ci-Cg-alkyl,
  • R 2 preferably represents in each case optionally substituted by halogen C -C2 () alkyl, C 2 -C20 alkenyl, -C-Cg-alkoxy-C2-Cg-alkyl, poly-C ⁇ -Cg-alkoxy-C2-Cg-alkyl .
  • C 3 -Cg-cycloalkyl optionally substituted by halogen, Ci-Cg-alkyl or Ci-Cg-alkoxy in which a ring atom is optionally replaced by oxygen, or
  • phenyl or benzyl optionally substituted by halogen, cyano, nitro, Ci-Cg-alkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkyl or Ci-Cg-haloalkoxy,
  • R 3 preferably represents Ci-Cg-alkyl optionally substituted by halogen or in each case optionally substituted by halogen, Ci-Cg-alkyl, Ci-Cg-alkoxy, Ci-C ⁇ -haloalkyl, Ci-C4-haloalkoxy, cyano or nitro Phenyl or benzyl,
  • R 4 and R5 are preferably, independently of one another, each optionally substituted by halogen-substituted Ci-Cg-alkyl, Ci-Cg-alkoxy, Ci-Cg-alkylamino, di- (Ci-Cg-alkyl) amino, Ci-Cg-alkylthio, C2 -Cg-alkenylthio, C 3 -C7-cycloalkylthio or for each optionally by halogen, nitro, cyano, C -C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkyl- thio, Ci-C4-haloalkylthio, Ci-C.4-Al.kyl or Ci-C4-haloalkyl substituted phenyl, phenoxy or phenylthio,
  • R6 and R 7 independently of one another preferably represent hydrogen, in each case optionally Ci-Cg-alkyl which is optionally substituted by halogen, C -Cg-cycloalkyl, Ci-Cg-alkoxy, C 3 -Cg-alkenyl, Ci-Cg-alkoxy-Ci - Cg-alkyl, for phenyl optionally substituted by halogen, Ci-Cg-halogeno-alkyl, Ci-Cg-alkyl or Ci-Cg-alkoxy, optionally by halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl or Ci-Cg Alkoxy-substituted benzyl or together for a C 3 -C 6 -alkylene radical which is optionally substituted by C 1 -C 4 -alkyl and in which one carbon atom is optionally replaced by oxygen or sulfur,
  • R 3 preferably represents Ci-C.4-Al.kyl or Ci-C-4-alkoxy which is optionally substituted by halogen or cyclopropyl or cyclohexyl which is optionally substituted by Ci-C2-alkyl or Ci-C2-alkoxy or
  • R 4 preferably represents hydrogen or C i -Cg-alkyl or
  • RI 3 and RI 4 together preferably represent C4-Cg-alkanediyl
  • Rl5 and R are the same or different and are preferably Ci-C4-alkyl or
  • Rl5 and R * together preferably represent a C2-C4-alkanediyl radical which is optionally substituted once to twice by Ci-C.4-alkyl,
  • R 7 and R ° are, independently of one another, preferably hydrogen, Ci-Cg-alkyl optionally substituted by halogen or optionally halogen, Ci-Cg-alkyl,
  • R 7 and RI8 together with the carbon atom to which they are attached preferably represent a carbonyl group or C5-C-cycloalkyl optionally substituted by C -C2-alkyl or Ci-C ⁇ -alkoxy, in which optionally a methylene group by oxygen or Sulfur is replaced,
  • Rl9 and R20 independently of one another preferably represent Ci-C4-Alk l, C2-C4-alkenyl, Ci-C.4-alkoxy, Ci-C4-alkylamino, C 3 -C4-alkenylamino, di- (Ci-C4-alkyl ) amino or di (C 3 -C 4 alkenyl) amino.
  • halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
  • X particularly preferably represents C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl, optionally optionally up to triple by fluorine, chlorine, bromine, C 1 -C 4 -alk l, C 1 -C 4 -alkoxy, C 1 -C 2 -haloalkyl, Ci-C2-haloalkoxy, nitro or cyano substituted phenyl,
  • C ⁇ -C preferably C-C4-alkyl, C ⁇ -C alkoxy, 4 -haloalkoxy or in each case optionally monosubstituted to disubstituted by C ⁇ -C 4 -alkyl, C alkoxy, fluorine, chlorine, bromine, CC 2 -Halogenalkyl, -CC 2 -haloalkoxy, cyano or nitro substituted benzyloxy or hetarylmethyloxy with 5 to 6 ring atoms (for example furanyl, pyridyl, pyrimidyl, thiazolyl, thienyl),
  • D particularly preferably represents hydrogen, in each case optionally mono- to trisubstituted by fluorine C Q -C - alkyl, C 3 -CG-alkenyl, Ci-Cg-alkoxy-Ci-C4-alkyl or C -CG-alkylthio-Ci-C4 -alkyl, for C 3 -C 7 -cycloalkyl which is optionally substituted simply by fluorine, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or C 1 -C 2 -haloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur or for in each case optionally by Fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C-4-alkoxy or Ci-C2-haloalkoxy substituted phenyl, or phenyl -CC 4 -alkyl or
  • a and D together particularly preferably represent optionally mono- to disubstituted C 3 -C5-alkanediyl or C 3 -C5 -alkenediyl, in which a methylene group can optionally be replaced by a carbonyl group, oxygen or sulfur, the substituents being hydroxy, C ⁇ - C 6 alkyl or CC 4 alkoxy are suitable,
  • G particularly preferably represents hydrogen (a) or one of the groups
  • E represents a metal ion equivalent or an ammonium ion
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • R particularly preferably represents Ci-C ig-alkyl, C2-Cig-alkenyl, Ci-Cg-alkoxy-Ci-C4-alkyl, Ci-Cg-alkylthio-Ci-C4- which is optionally mono- to pentas substituted by fluorine or chlorine. alkyl or optionally single to double by fluorine, chlorine,
  • Ci-C-4- alkyl for optionally single to double by fluorine, chlorine, bromine, cyano, nitro, Ci-C-4- alkyl, Ci-C4-alkoxy, C -C 3 haloalkyl, -C-C 3 haloalkoxy, Ci-C-4- Alkylthio or
  • phenyl-Ci-C.4-alkyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine, Ci-C-alkyl, C - -j- alkoxy, Ci-C 3 -haloalkyl or Ci-C 3 -haloalkoxy, for in each case, if appropriate, once to twice by fluorine, chlorine, bromine Trifluoromethyl or Ci-C2-alkoxy substituted pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl,
  • R 2 particularly preferably represents in each case optionally up to five times substituted by fluorine-substituted C i -C i alkyl, C2 -C i alkenyl or C -C alkoxy-C2-Cg alkyl,
  • C 3 -C 7 -cycloalkyl which is optionally mono- to disubstituted by fluorine, chlorine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy or
  • phenyl or phenyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine, cyano, nitro, Ci-C.4-Al.kyl, Ci-C 3 -alkoxy, Ci-C2 ⁇ haloalkyl or Ci-C2-haloalkoxy benzyl,
  • R 3 particularly preferably represents C 1 -C 6 -alkyl which is optionally monosubstituted to pentasubstituted by fluorine or optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, C 1 -C 4 -alk 1, C 4 -C 4 -alkoxy, C 1 -C 3 Haloalkyl, Ci-C 3 -haloalkoxy, cyano or nitro substituted phenyl,
  • R 4 particularly preferably represents Ci to Cg-alkyl, Ci-Cg-alkoxy, Ci-Cg-alkylamino, di- (Ci-Cg-alkyl) amino, Ci-Cg-alkylthio, C, which is optionally mono- to trisubstituted by fluorine 3 -C4-Alkenylthio, C 3 -Cg-Cycloalkylthio or for each optionally optionally up to twice by fluorine, chlorine, bromine, nitro, cyano, C -C 3 -alkoxy, Ci-C 3 -haloalkoxy, Ci-C 3 -alkylthio Ci-C 3 haloalkylthio, Ci-C 3 alkyl or Ci-C 3 haloalkyl substituted phenyl, phenoxy or phenylthio,
  • R ⁇ particularly preferably represents C i -Cg alkoxy or C i -Cg alkylthio
  • R 7 particularly preferably represents hydrogen, Ci-Cg-alkyl, C 3 -Cg-alkenyl, or R and R 7 particularly preferably together represent a C4-C5alkylene radical which is optionally mono- to disubstituted by methyl or ethyl and in which a methylene group is optionally replaced by oxygen or sulfur.
  • halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
  • X very particularly preferably represents methyl, ethyl, propyl, trifluoromethyl, optionally optionally one to two times by fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, isopropyl, tert-butyl, trifluoromethoxy, methoxy, ethoxy, isopropoxy, tert.- Butoxy, cyano or nitro substituted phenyl,
  • Y very particularly preferably represents hydrogen in the case of het (1-3) or methyl
  • Z very particularly preferably represents methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy or trifluoroethoxy,
  • D very particularly preferably represents hydrogen, in each case methyl, ethyl, allyl which is optionally monosubstituted to trisubstituted by fluorine or optionally fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy or trifluoromethyl which is monosubstituted or substituted twice or trifluoromethoxy substituted phenyl,
  • a and D together very particularly preferably represent optionally substituted C 3 -C 5 -alkanediyl, in which one carbon atom is optionally replaced by oxygen and which is optionally mono- to disubstituted by methyl, ethyl, methoxy or ethoxy, G very particularly preferably represents hydrogen (a) or one of the groups
  • E represents a metal ion equivalent or an ammonium ion
  • L represents oxygen or sulfur
  • M oxygen or sulfur
  • R very particularly preferably represents in each case mono- to trisubstituted by fluorine-substituted C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl, C 1 -C 2 -alkylthio-C 1 -C 2 alkyl or in each case optionally cyclopropyl, cyclopentyl or cyclohexyl which is simply substituted by fluorine, chlorine, methyl, ethyl or methoxy,
  • phenyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
  • R 2 very particularly preferably represents Ci to Cg-alkyl, C2-Cg-alkenyl or C 1 -C 4 -alkoxy-C2-C-alkyl which is optionally mono- to trisubstituted by fluorine,
  • cyclohexyl optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or methoxy
  • R 3 very particularly preferably represents methyl, ethyl, n-propyl or phenyl which is monosubstituted by fluorine, chlorine, bromine, methyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
  • R 4 very particularly preferably represents in each case optionally mono- to trisubstituted by fluorine-substituted Ci-d- j alkyl, Ci-C4-alkoxy, Ci-C4-alkylamino, di- (Ci-G4-alkyl) amino,
  • R very particularly preferably represents methoxy, ethoxy, methylthio or ethylthio
  • R ⁇ very particularly preferably represents in each case mono- to trisubstituted by fluorine-substituted Ci-C.4-Al.kyl, C 3 -Cg-cycloalkyl, Ci-C.4-alkoxy, C -C4-alkenyl, C -C. 4- alkoxy-C 1 -C 4 -alkyl, for phenyl optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, methyl or methoxy, for benzyl optionally substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy,
  • R 7 very particularly preferably represents hydrogen, methyl, ethyl, propyl or allyl or
  • R ⁇ and R 7 very particularly preferably stand for a C5-Cg-alkylene radical in which a methylene group is optionally replaced by oxygen or sulfur.
  • X stands for optionally one to two times by fluorine, chlorine, bromine,
  • Y stands for hydrogen in the case of Het (1-3) or methyl, ethyl or propyl in the case of Het (1-1),
  • Z stands for methyl, ethyl, propyl or isopropyl
  • A stands for methyl or ethyl
  • D stands for methyl or ethyl
  • a and D stand out for C 3 -C 5 -alkanediyl, in which a carbon atom is optionally replaced by an oxygen atom,
  • G stands for hydrogen (a) or for one of the groups
  • Rl stands for Ci-Cg-alkyl, C2-C4-alkenyl, Ci-C2-alkoxy-C ⁇ -C2-alkyl, C ⁇ -C2-alkylthio-Ci-C2-alk l, cyclopropyl or cyclohexyl,
  • phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, tert-butoxy, trifluoromethyl or trifluoromethoxy,
  • R 2 stands for Ci-Cg-alkyl, C2-C4-alkenyl or Ci-C4-alkoxy-C2-C 3 -alkyl
  • X in particular represents phenyl which is optionally monosubstituted by chlorine
  • Y stands in particular for hydrogen in the case of Het (1-3) or methyl or propyl in the case of Het (1-1),
  • Z stands in particular for methyl
  • a and D are in particular C 3 -C 5 -alkanediyl, in which a carbon atom is optionally replaced by an oxygen atom,
  • G in particular represents hydrogen (a) or one of the groups
  • Rl in particular represents Ci-Cg-alkyl
  • R 2 stands in particular for Ci-Cg-alkyl.
  • Saturated or unsaturated hydrocarbon residues such as alkyl or alkenyl can also be used in connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.
  • optionally substituted radicals can be mono- or polysubstituted, and in the case of multiple substitutions the substituents can be the same or different.
  • substituents can be the same or different.
  • the following compounds of the formula (Ila) may be mentioned.
  • herbicide safeners of the formulas (Ila), (Db), (He), (Ild) and (He) which improve crop plant tolerance are defined below ,
  • n preferably represents the numbers 0, 1, 2, 3 or 4.
  • a 1 preferably represents one of the divalent heterocyclic groups outlined below
  • a 2 preferably represents methylene or ethylene which is optionally substituted by methyl, ethyl, methoxycarbonyl or ethoxycarbonyl.
  • R 22 preferably represents hydroxy, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i -, s- or t-butylthio,, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino.
  • R 23 preferably represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine, chlorine and / or bromine.
  • R 24 preferably represents hydrogen, in each case optionally substituted by fluorine and / or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, Ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl, piperidinyl, or optionally by fluorine, chlorine,
  • R 25 preferably represents hydrogen, in each case optionally substituted by fluorine and or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl , Methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl, piperidinyl, or optionally by fluorine, chlorine,
  • R 26 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl, each optionally substituted by fluorine, chlorine and or bromine.
  • R 27 preferably represents hydrogen, optionally substituted by hydroxy, cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy methyl, ethyl, n- or i-propyl, n-, i-, s- or t- butyl.
  • R 28 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine, chlorine and or bromine , Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.
  • X 1 preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoro- meth-yl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
  • X 2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl , Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
  • X 3 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl , Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
  • R 29 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
  • R 30 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
  • R 31 preferably represents hydrogen, in each case optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-
  • R 32 preferably represents hydrogen, in each case optionally substituted by cyano, hydroxy, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propynyl or butinyl, each optionally substituted by cyano, fluorine, chlorine or bromine, or in each case optionally by cyano, fluorine, chlorine,
  • R 33 preferably represents hydrogen, in each case optionally through cyano, hydroxy, fluorine, chlorine,
  • Methoxy, ethoxy, n- or i-propoxy substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, in each case propenyl optionally substituted by cyano, fluorine, chlorine or bromine,
  • X 4 preferably represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
  • X 5 preferably represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl,
  • crop plant compatibility-improving compound [component (b)] are cloquintocet-mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron, dimepiperate and the compounds He-5 and He-l 1 most preferred, with Cloquintocet-mexyl and Mefenpyr-diethyl being particularly emphasized.
  • the compounds of the general formula (Hb) to be used according to the invention as safeners are known and / or can be prepared by processes known per se (cf. EP-A-191736).
  • the compounds of the general formula (Hc) to be used as safeners according to the invention are known and / or can be prepared by processes known per se (cf. DE-A-2218097, DE-A-2350547).
  • halocarbonyl ketene of the formula (III) required as starting materials in the above processes (A- ⁇ ) are new. They can be prepared in a simple manner by methods known in principle (cf. for example Org. Prep. Proced. Int., 7, (4), 155-158, 1975, WO 96/35664, WO 97/02243, WO 97 / 36868 and DE 1 945 703).
  • acid halides such as, for example, thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, oxalyl chloride, phosgene or thionyl bromide, if appropriate in the presence of catalysts, such as, for example, diethylformamide, methyl-sterylformamide or triphenylphosphine and, if appropriate, in the presence of bases such as, for example Pyridine or triethylamine.
  • acid halides such as, for example, thionyl chloride, phosphorus (V) chloride, phosphorus (III) chloride, oxalyl chloride, phosgene or thionyl bromide
  • catalysts such as, for example, diethylformamide, methyl-sterylformamide or triphenylphosphine and, if appropriate, in the presence of bases such as, for example Pyridine or triethylamine.
  • the substituted phenylmalonic acids of the formula (IV-a) are new. They can be produced in a simple manner by known processes (cf., for example, Organikum, VEB German Publishing House of Sciences, Berlin 1977, pp. 517 ff, EP-A-528 156, WO 96/35 664, WO 97/02 243, WO 97/01535, WO 97/36868 and WO 98/05638).
  • R 8 represents alkyl
  • Het and R 8 have the meaning given above, are new with the exception of (1,3,5-trimethyl-1H-pyrazolyl) malonic acid diethyl ester and [1- (2,4-dinitrophenyl) -3,5-dimethyl-1H-pyrazol-4-yl] malonic acid diethyl ester (Alberola et al., Anales de Quimica, Srie C: Quimica Organica y Bioquimica, 83, 55-61, 1987).
  • hetaryl acid esters of the formula (XVD) are commercially available, some are known or can be prepared by processes known in principle
  • N-pyrazolylacetic acid esters of the formula (XVI) are known (DE-A 10 152 005). They can be prepared by processes known in principle (Nam, N.L. et. Al, Chemistry of Heterocyclic Compounds 34, 382, (1998); L.K. Kulihova, L.V. Cherkesova, Khimiko-Farmateseyticheskii Zhurnal, 8, 18-21, (1974)).
  • carboxylic acid activation reagents such as carbonyldiimidazole, carbonyldiimides (such as dicyclohexylcarbondiimide), phosphorylation reagents (such as
  • halogenating agents for example thionyl chloride, oxalyl chloride, phosgene or
  • the compounds of formula (XVIII) are partly new. They can be prepared by methods known in principle and as can be seen from the preparation examples (see, for example, H. Henecka, Houben-Weyl, Methods of Organic Chemistry, Vol. 8, pp. 467-469 (1952)).
  • halogenating agents for example thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride
  • phosphonylating reagents such as (for example POCl 3 , BOP-Cl), carbonyldiimidazole, carbonyldiimides (for example dicyclohexyl carbonate), if appropriate in the presence of a (eg or aromatic hydrocarbons such as toluene or methylene chloride or ethers, for example tetrahydrofuran, dioxane, methyl tert-butyl ether) at temperatures of from -20 ° C. to 150 ° C., preferably from -10 ° C. to 100 ° C.
  • a eg or aromatic hydrocarbons such as toluene or methylene chloride or ethers, for example te
  • hetarylacetic acids of the formula (XIX) are commercially available, some are known or can be prepared by the processes known in principle, which were also mentioned for the preparation of the compounds of the formula (XVI).
  • the carbazates of the formula (XV-Q) are some commercially available and some known compounds or can be prepared by processes known in principle in organic chemistry.
  • Process (A- ⁇ ) according to the invention is characterized in that hydrazines of the formula (II) or salts of these compounds are reacted with ketonic acid halides of the formula (TU) in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.
  • Chlorinated hydrocarbons such as, for example, mesitylene, chlorobenzene and dichlorobenzene, toluene, xylene
  • further ether such as dibutyl ether, glycol dimethyl ether, diglycol dimethyl ether and diphenylethane
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or N-methylpyrrolidone
  • All customary acid acceptors can be used as acid acceptors when carrying out process variant (A- ⁇ ) according to the invention.
  • Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecane (DBU), diazabicyclonones (DBN), Hunig base and N, N-dimethyl-aniline can preferably be used.
  • reaction temperatures can be carried out when the inventive compounds
  • Process variant (A- ⁇ ) can be varied within a wide range. It is expedient to work at temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 220 ° C. Process (A- ⁇ ) according to the invention is advantageously carried out under normal pressure.
  • reaction components of the formulas (ET) and (DI), in which A, D and Het have the meanings given above and Hai is halogen, and, if appropriate, the acid acceptors in general are set in about equimolar amounts.
  • the process (A-ß) is characterized in that hydrazines of the formula (II) or salts of this compound, in which A and D have the meanings given above, with malonic acid derivatives of the formula (IV), in which Het and R ° the have the meaning given above, is subjected to condensation in the presence of a base.
  • Halogenated hydrocarbons such as toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, diphenyl ether, glycol dimethyl ether and diglycol dimethyl ether, and also polar solvents such as dimethyl sulfoxide, sulfolane and dimethyl formamide, dimethylformamide, Methyl pyrrolidone, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • All conventional proton acceptors can be used as the base (deprotonating agent) when carrying out the process (A- ⁇ ) according to the invention.
  • Alkali metals such as sodium or potassium can also be used.
  • Alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can also be used.
  • reaction temperatures can be varied within a substantial range when carrying out process (A- ⁇ ) according to the invention. In general, temperatures between 0 ° C and 280 ° C, preferably between 50 ° C and 180 ° C.
  • the process according to the invention (A- ⁇ ) is generally carried out under normal pressure.
  • reaction components of the formulas (II) and (IV) are generally employed in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 mol).
  • the process (A- ⁇ ) is characterized in that compounds of the formula (V) in which A, D, Het and R ° have the meanings given above are subjected to an intramolecular condensation in the presence of a base.
  • All inert organic solvents can be used as diluents in process (A- ⁇ ) according to the invention.
  • Hydrocarbons such as toluene and xylene, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and also polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone, and alcohols such as methanol, ethanol, propanol, are preferably usable. Iso-propanol, butanol, iso-butanol and tert-butanol.
  • All conventional proton acceptors can be used as the base (deprotonating agent) when carrying out process (A- ⁇ ) according to the invention.
  • Alkali metals such as sodium or potassium can also be used.
  • Alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can also be used.
  • reaction temperatures can be varied within a substantial range when carrying out process (A- ⁇ ) according to the invention. In general, temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.
  • the process (A- ⁇ ) according to the invention is generally carried out under normal pressure.
  • reaction components of the formula (V) and the deprotonating bases are generally employed in approximately double-equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 moles).
  • Process (B- ⁇ ) is characterized in that compounds of the formulas (I-l-a) to (I-4-a) are each reacted with carboxylic acid halides of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Diluents which can be used in process (B- ⁇ ) according to the invention are all solvents which are inert to the acid halides.
  • Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin, more preferably halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, and furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxan in addition carboxylic acid esters such as ethyl acetate, nitriles such as acetonitrile and also strongly polar solvents such as dimethylformamide, dimethyl acetamide, dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can also be carried
  • Suitable acid binders for the reaction according to process (B- ⁇ ) according to the invention are all customary acid acceptors.
  • Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DB), Hunig base and N, N-dimethylaniline, and furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, are also preferably usable Alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • reaction temperatures can be varied within a substantial range in the process (B- ⁇ ) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
  • process (B- ⁇ ) When carrying out process (B- ⁇ ) according to the invention, the starting materials of the formulas (Ila) to (I-4-a) and the carboxylic acid halide of the formula (VI) are generally in each case used in approximately equivalent amounts. However, it is also possible to use the carboxylic acid halide in a larger excess (up to 5 mol).
  • the processing takes place according to usual methods.
  • Process (B- ⁇ ) is characterized in that compounds of the formulas (Ila) to (I-4-a) are reacted with carboxylic anhydrides of the formula (VII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • the diluents which can be used in the process (B- ⁇ ) according to the invention are preferably those diluents which are also preferred when using acid halides.
  • an excess of carboxylic acid anhydride can also act as a diluent.
  • Suitable acid binders which may be added in process (B- ⁇ ) are preferably those acid binders which are also preferred when using acid halides.
  • reaction temperatures can be varied within a substantial range in the process (B- ⁇ ) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
  • the starting materials of the formulas (I-l-a) to (I-4-a) and the carboxylic anhydride of the formula (VII) are generally used in approximately equivalent amounts in each case. However, it is also possible to use the carboxylic anhydride in a larger excess (up to 5 mol). The processing takes place according to usual methods.
  • the general procedure is to remove diluent and excess carboxylic anhydride and the carboxylic acid formed by distillation or by washing with an organic solvent or with water.
  • Process (C) is characterized in that compounds of the formulas (I-l-a) to (I-4-a) are each reacted with chloroformic acid esters or chloroformic acid thiolesters of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable acid binders for the reaction according to process (C) according to the invention are all customary acid acceptors.
  • Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and N, N-dimethylaniline
  • alkaline earth metal oxides such as magnesium and calcium oxide
  • alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate
  • Diluents which can be used in process (C) according to the invention are all solvents which are inert to the chloroformates or chloroformates.
  • Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin, preferably also halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, hydrogen, chlorobenzene and o-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, and furthermore ethers, such as diethyl ether, are preferably usable.
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, hydrogen, chlorobenzene and o-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, and furthermore ethers, such as diethyl ether, are preferably usable.
  • Tetrahydrofuran and dioxane in addition carboxylic acid esters such as ethyl acetate, nitriles such as acetonitrile and also strongly polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide and sulfolane.
  • carboxylic acid esters such as ethyl acetate
  • nitriles such as acetonitrile
  • strongly polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide and sulfolane.
  • reaction temperatures can be varied within a substantial range when carrying out process (C) according to the invention. If one works in the presence of a diluent and an acid binder, the reaction temperatures are generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.
  • Process (C) according to the invention is generally carried out under normal pressure.
  • the starting materials of the formulas (Ila) to (I-4-a) and the corresponding chloroformic acid ester or chloroformic acid thiolester of the formula (VH) are generally in each case used in approximately equivalent amounts. However, it is it is also possible to use one or the other component in a larger excess (up to 2 mol).
  • the working up is carried out according to customary methods. In general, the procedure is to remove precipitated salts and to concentrate the remaining reaction mixture by stripping off the diluent ,
  • Process (D) according to the invention is characterized in that compounds of the formulas (I-l-a) to (I-4-a) are each reacted with compounds of the formula (TX) in the presence of a diluent and, if appropriate, in the presence of an acid binder.
  • chloromothio formate or chlorodithio formate of formula (IX) is set at 0 to 120 ° C., preferably at 20 to 60 ° C., per mole of starting compound of the formulas (Ila) to (I-4-a) around.
  • Possible diluents added are all inert polar organic solvents, such as nitriles, esters, ethers, amides, sulfones, sulfoxides, but also haloalkanes.
  • Acetonitrile, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably used.
  • the enolate salt of the compounds (Ila) to (I-4-a) is represented by the addition of strong deprotonating agents such as sodium hydride or potassium tert-butoxide, the further addition of acid binders can be dispensed with.
  • acid binders customary inorganic or organic bases are possible, examples being sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
  • the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
  • the processing takes place according to usual methods.
  • Process (E) is characterized in that compounds of the formulas (I-l-a) to (I-4-a) are each reacted with sulfonyl chlorides of the formula (X), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • any inert polar organic solvents such as nitriles, esters, ethers, amides, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride are suitable as diluents which may be added.
  • Acetonitrile, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, methylene chloride are preferably used.
  • the enolate salt of the compounds (I-1-a) to (I-4-a) is prepared by adding strong deprotonating agents (such as sodium hydride or potassium tert-butoxide), the further addition of acid binders can be dispensed with.
  • strong deprotonating agents such as sodium hydride or potassium tert-butoxide
  • acid binders customary inorganic or organic bases are possible, examples being sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
  • the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
  • the processing takes place according to usual methods.
  • Process (F) according to the invention is characterized in that compounds of the formulas (I-l-a) to (I-4-a) are each reacted with phosphorus compounds of the formula (XI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Possible diluents added are all inert, polar organic solvents such as ethers, amides, nitriles, alcohols, sulfides, sulfones, sulfoxides etc.
  • Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, methylene chloride are preferably used.
  • Possible inorganic binders which may be added are conventional inorganic or organic bases, such as hydroxides, carbonates or amines. Examples include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
  • the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
  • the processing takes place according to the usual methods of organic chemistry.
  • the end products obtained are preferably purified by crystallization, chromatographic purification or by so-called “distillation", i.e. Removal of volatiles in vacuo.
  • Process (G) is characterized in that compounds of the formulas (Ila) to (I-4-a) are reacted with metal hydroxides or metal alkoxides of the formula (Xu) or amines of the formula (XIH), if appropriate in the presence of a diluent ,
  • Diluents which can be used in process (G) according to the invention are preferably ethers such as tetrahydrofuran, dioxane, diethyl ether or alcohols such as methanol, ethanol, isopropanol, but also water.
  • Process (G) according to the invention is generally carried out under normal pressure.
  • the reaction temperatures are generally between -20 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.
  • Process (H) is characterized in that compounds of the formulas (Ila) to (I-4-a) in each case (H- ⁇ ) with compounds of the formula (XIV), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst or (H-ß) with compounds of the formula (XV) if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Possible diluents added are all inert organic solvents, such as ethers, amides, nitriles, sulfones, sulfoxides.
  • catalysts can be added to accelerate the reaction.
  • Organotin compounds such as e.g. Dibutyltin dilaurate can be used. It is preferably carried out at normal pressure.
  • Possible diluents added are all inert polar organic solvents, such as nitriles, esters, ethers, amides, sulfones, sulfoxides or halogenated hydrocarbons.
  • Acetonitrile, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene chloride are preferably used.
  • the enolate salt of the compound (I-1-a) to (I-4-a) is prepared by adding strong deprotonating agents (such as sodium hydride or potassium tert-butoxide), the further addition of acid binders can be dispensed with.
  • strong deprotonating agents such as sodium hydride or potassium tert-butoxide
  • customary inorganic or organic bases are suitable, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
  • the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
  • the processing takes place according to usual methods.
  • the active ingredients are suitable for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture Forests, in gardens and leisure facilities, in the protection of supplies and materials as well as in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
  • Thysanoptera for example Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
  • Heteroptera for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Homoptera e.g
  • Otiorrhynchus sulcatus Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderas spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptras oryzophilus.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.
  • Plant parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
  • Plant parts are to be understood to mean all above-ground and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, for example by dipping, spraying, evaporating, atomizing, scattering, spreading, lijezing and in the case of propagation material, in particular seeds. continue by wrapping one or more layers.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to spread the spectrum of activity or to prevent the development of resistance.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • 2-Phenyl ⁇ henol 8-hydroxyquinoline sulfates; Acibenzolar-S-methyl; Aldimo h; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin;
  • bilanafos binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate;
  • Flubenzimine Flubenzimine; fludioxonil; flumetover; Flumo ⁇ h; fluoromides; fluoxastrobin; fluquinconazole;
  • flurprimidol flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium;
  • fuberidazole furalaxyl; furametpyr; Furcarbanil; Furmecyclox; guazatine; Hexachlorobenzene; hexaconazole; hymexazol; imazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadme tris (albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; -rumamycin;
  • isoprothiolane Isovaledione; kasugamycin; Kresoxim-methyl; mancozeb; maneb; Meferimzone;
  • mepanipyrim mepronil; metalaxyl; Metalaxyl-M; metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline; natamycin;
  • nicobifen Nitro Thal-isopropyl; Noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin; paclobutrazol; Pefurazoate; penconazole;
  • Thicyofen Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; Tridemo ⁇ h;
  • trifloxystrobin triflumizole; triforine; triticonazole; Uniconazole; Validamycin A; vinclozolin;
  • copper salts and preparations such as Bordeaux mixture; Copper hydroxide; Copper naphthenate; Copper oxychloride; Copper sulfates; Cufraneb; Cuprous oxide; mancopper; Oxine-copper.
  • DDT Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinone, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimefluthrin, Dimethoate, Dinobutyl, Dinobutinophone, Dimobutinophone Disulfoton, Docusat-sodium, Dofenapyn, DOWCO-439,
  • Gamma-cyhalothrin gamma-HCH, gossyplure, grandlure, granulovirus
  • Halofenozide HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydra-methylnone, Hydroprene,
  • Mecarbam Mesulfenfos, Metaldehyde, Metam-sodium, Methacrifos, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathion, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metofluthrin, Metolcarb, Metevinphinbone, Milevinbine, Miloxcinphin, MK, Metoxinphinzone MK MON-45700, Monocrotophos, Moxidectin, MTI-800,
  • NC-104 NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,
  • Paecilomyces fiimosoroseus Parathion-methyl, Parathion (-ethyl), Permethrin (eis, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, Pirimiphos-methyl, Pirimiphos-ethyl, Potassium oleate, Prallethrin, Profenofos, Profluthrin, Promecarb, Propaphos, Propargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetclhrosine, Pymetclhrosine, Pymetrohrosine Pyridaben, Pyridalyl, Pyridaphenthion, Pyridathion, Pyrimidifen, Pyrip
  • the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with inhibitors which break down the active compound after use in the environment of the plant, on the surface of parts of plants or in plant tissues Reduce.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active substance When used against hygiene pests and pests of stored products, the active substance is distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • all plants and their parts can be treated.
  • wild plant species or plant species and their parts obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods if appropriate in combination with conventional methods (genetic modified organisms) and their parts are treated.
  • the term "parts” or “parts of plants” or “plant parts” was explained above.
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant cultivars are understood as meaning plants having novel properties ( "traits”), 'which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes.
  • the treatment according to the invention can also cause superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and / or widening of the spectrum of action and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance , easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvest products, higher storability and / or workability of the harvest products possible, which go beyond the expected effects.
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, through the genetic engineering modification, have received genetic material which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, higher harvest yields, higher quality and / or higher mowing value of the crop products, higher shelf life and / or workability of the crop products.
  • transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus loads and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed are highlighted.
  • the traits that are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (a) , CryIA (b), Cry ⁇ A (c), Cry-QA, Cryl-EA, Cryi ⁇ B2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants”).
  • the properties (“traits”) also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • the properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene).
  • the genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
  • Bt plants are maize varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD GARD® e.g. corn, cotton, soy
  • KnockOut® e.g. corn
  • StarLink® e.g. corn
  • Bollgard® Cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g.
  • rapeseed rapeseed
  • HVH® tolerance to Pmidazolinone
  • STS® tolerance to sulfonylureas such as maize
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
  • plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention.
  • the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants.
  • Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
  • the active compounds according to the invention act not only against pests from plants, hygiene and stored products, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair lice, Featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtiras spp., Solenopotes spp ..
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp.,
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophoras spp., Acaras spp.
  • Tyrophagus spp. Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are used in agricultural animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice.
  • arthropods By combating these arthropods, deaths and reduced performance (in meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.
  • the active compounds according to the invention are used in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), des Washing, the powder and with the help of shaped bodies containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories
  • parenteral administration for example by Injections (
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
  • Wood and wood processing products that can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
  • the active compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and, if appropriate Dyes and pigments and other processing aids.
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimum amount of use can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, Te ⁇ entinöl and Like. Used.
  • liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochloronaphthalene, preferably ct-monochloronaphthalene, are used.
  • the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
  • Aliphatic organochemical solvents containing hydroxyl and / or ester and / or ether groups such as, for example, glycol ethers, esters or the like, are preferably used.
  • the organic-chemical binders used are the water-thinnable synthetic resins which are known per se and / or which are soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.
  • binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as butyl stearate or amyl
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • the ready-to-use compositions may optionally contain further insecticides and, if appropriate, one or more fungicides.
  • the insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional mixing partners.
  • the links mentioned in this document are an integral part of this application.
  • Insecticides such as Chlo ⁇ yriphos, Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin, Permethrin, Imidacloprid, NI-25, Flufenoxuron, Hexaflumuron, Transfluthrin, Methoxyphenidlopin, Trifluoridophenol, Trifluoridophenol, Trifluoride
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro octylisothiazolin-3-one.
  • the compounds according to the invention can be used to protect objects, in particular hulls, screens, nets, networks, structures, quay systems and signaling systems which come into contact with sea or brackish water.
  • Ledamo ⁇ ha barnacles
  • Balanomo ⁇ ha barnacles
  • Baianus or Pollicipes species increases the frictional resistance of Ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.
  • heavy metals such as e.g. in bis (trialkyltin) sulfides, tri-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulfide, Antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri - «- butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridinethiol-1-oxide, bisdimethyldihydiamethyldihydiamethyldihydiamethyldihydiamethyldihydiamethyldihydiamethyldihyd
  • the ready-to-use antifouling paints can optionally contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.
  • Suitable combination partners for the antifouling agents according to the invention are preferably:
  • Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as
  • antifouling agents such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nit ⁇ othiazyl, potassium, copper, sodium and zinc salts of 2-pyridine thiol -l-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachloroiso ⁇ hthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichloro-phenylmaleimide ,
  • the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.
  • the antifouling agents according to the invention further contain the usual ingredients such as in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • antifouling paints contain in particular binders.
  • Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride-vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.
  • Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in seawater.
  • paints may contain materials such as rosin to enable controlled release of the active ingredients.
  • the paints may also contain plasticizers, modifiers affecting theological properties, and other conventional ingredients.
  • the compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
  • the active ingredients are also suitable for controlling animal pests, in particular of
  • Sco ⁇ ionidea e.g. Buthus occitanus.
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodoras moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridium, Opiliones phalangium.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • the active compounds according to the invention can also be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can e.g. can be used in the following plants:
  • the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the active compounds according to the invention for weed control in permanent crops e.g. Forests, ornamental trees, fruit, wine, citras, nuts, bananas, coffee, tea, rubber, oil palm, cocoa, berry freight and hop systems, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
  • the compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.
  • the active compounds according to the invention can also be used to control animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or products for the synthesis of further active ingredients.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known herbicides and / or with substances which improve crop tolerance (“safenem”) for weed control, ready-to-use formulations or tank mixes being possible. Mixtures are therefore also possible possible with weed control agents which contain one or more known herbicides and a safener.
  • safenem crop tolerance
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents improving soil structure is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are usually used, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
  • Example I-l-a-1 The oil was used in the synthesis of Example I-l-a-1 without further purification.
  • Test insect Diabrotica balteata - larvae in the soil
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • the active ingredient preparation is poured onto the floor.
  • the concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and populated with the tobacco bud caterpillar Heliothis virescens while the leaves are still moist.
  • the killing of the insects is determined.
  • Test compounds formulated in the form of emulsion concentrates (EC) are applied in various dosages with a water application rate of the equivalent of 8001 / ha with the addition of wetting agents to the surface of the covering earth.
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Chinese cabbage leaf slices (Brassica pekinensis), which are affected by all stages of the green peach aphid (Myzus persicae), are sprayed with an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all aphids have been killed, 0% means that no aphids have been killed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

La présente invention concerne des dérivés de pyrazolidine à substitution hétaryl, représentés par la formule (I), dans laquelle Het, A, D et G ont la signification donnée dans le descriptif, plusieurs procédés de fabrication de ces dérivés, et leur utilisation en tant qu'agents pesticides et/ou herbicides. L'invention concerne également des herbicides sélectifs contenant d'une part des dérivés de pyrazolidine-dione à substitution hétaryl et d'autre part un composé améliorant la compatibilité desdits herbicides avec des plantes de culture.
EP04763173A 2003-07-14 2004-07-12 Derives de pyrazolidine-dione a substitution hetaryl avec les caracteristiques d'herbicides Withdrawn EP1648898A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10331675A DE10331675A1 (de) 2003-07-14 2003-07-14 Hetarylsubstituierte Pyrazolidindion-Derivate
PCT/EP2004/007665 WO2005005428A1 (fr) 2003-07-14 2004-07-12 Derives de pyrazolidine-dione a substitution hetaryl avec les caracteristiques d’herbicides

Publications (1)

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EP1648898A1 true EP1648898A1 (fr) 2006-04-26

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US (1) US7420062B2 (fr)
EP (1) EP1648898A1 (fr)
JP (1) JP2007526892A (fr)
CN (1) CN100482666C (fr)
BR (1) BRPI0412552A (fr)
DE (1) DE10331675A1 (fr)
WO (1) WO2005005428A1 (fr)

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CN100482666C (zh) 2009-04-29
JP2007526892A (ja) 2007-09-20
CN1849321A (zh) 2006-10-18
DE10331675A1 (de) 2005-02-10
BRPI0412552A (pt) 2006-09-19
WO2005005428A1 (fr) 2005-01-20
US7420062B2 (en) 2008-09-02
US20070066488A1 (en) 2007-03-22

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